CN115178275A - Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst, preparation thereof and method for preparing furfural by catalyzing corncobs - Google Patents
Core-shell structure M X O y @mSiO 2 -SO 3 H-type catalyst, preparation thereof and method for preparing furfural by catalyzing corncobs Download PDFInfo
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- CN115178275A CN115178275A CN202210646607.1A CN202210646607A CN115178275A CN 115178275 A CN115178275 A CN 115178275A CN 202210646607 A CN202210646607 A CN 202210646607A CN 115178275 A CN115178275 A CN 115178275A
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000011258 core-shell material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
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- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- 239000012074 organic phase Substances 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 15
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 15
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 10
- 240000008042 Zea mays Species 0.000 description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 9
- 235000005822 corn Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
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- 235000006408 oxalic acid Nutrition 0.000 description 7
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- 238000000926 separation method Methods 0.000 description 6
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- 238000010533 azeotropic distillation Methods 0.000 description 5
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229920001221 xylan Polymers 0.000 description 2
- 150000004823 xylans Chemical class 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- -1 sulfhydryl peroxide Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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Abstract
Core-shell structure M x O y @mSiO 2 ‑SO 3 An H-type catalyst, a preparation method thereof and a method for preparing furfural by catalyzing corncobs. The invention belongs to the field of furfural preparation by biomass. The invention aims to solve the technical problems of low catalytic efficiency and low furfural yield of the existing Core-shell type catalyst for catalyzing corncobs to generate furfural. The invention relates to a core-shell structure M x O y @mSiO 2 ‑SO 3 The H-type catalyst core is spherical metal oxide M x O y The shell is sulfonated mesoporous SiO 2 . The method comprises the following steps: step 1: preparation of metallic oxygenA compound; and 2, step: preparation of M x O y @mSiO 2 (ii) a And 3, step 3: purifying and grafting MPTMS; and 4, step 4: preparation M x O y @mSiO 2 ‑SO 3 H. The application comprises the following steps: adopts a core-shell structure M x O y @mSiO 2 ‑SO 3 The H-type catalyst catalyzes the corncobs to prepare the furfural. The catalyst of the invention is of a core-shell nano structure, M x O y @mSiO 2 ‑SO 3 The shape of H is regular, the hydrothermal stability of the shell is good, the diacid active sites are effectively combined through the core-shell structure, the synergistic effect is maximized, the efficiency and the yield of catalyzing the corncobs to produce the furfural are remarkably improved, and the yield of the furfural can be kept at 74.2% after the corncobs are repeatedly utilized for 10 times.
Description
Technical Field
The invention belongs to the field of furfural preparation by biomass, and particularly relates to a core-shell structure M x O y @mSiO 2 -SO 3 An H-type catalyst, a preparation method thereof and a method for preparing furfural by catalyzing corncobs.
Background
The biomass resource can produce a plurality of high value-added products, such as furfural, polyester, adhesive and the like. Furfural is an important bio-based platform chemical substance, and is directly or indirectly synthesized into thousands of chemical products through hydrogenation, oxidative dehydrogenation, esterification, halogenation, polymerization, hydrolysis and other chemical reactions, and is widely applied to a plurality of fields of food, medical treatment, chemical industry and the like. Furfural, one of the non-petroleum derived chemicals, is not synthesized by an effective chemical method at present, but is obtained by converting xylan in hemicellulose. Xylan in hemicellulose is hydrolyzed under the action of acid to generate xylose, and then the xylose is subjected to isomerization and continuous three-step dehydration reaction to generate furfural.
The catalyst for preparing furfural can be divided into homogeneous catalysts and heterogeneous catalysts (solid acid catalysts). The homogeneous catalyst comprises H 2 SO 4 、HCl、H 3 PO 4 、CH 3 The yield of furfural prepared from the corn cobs by homogeneous acid catalysis of COOH, metal chloride, acidic ionic liquid and the like is usually 50-70%. Although the homogeneous acid has low cost, the homogeneous acid is easy to corrode reaction equipment, the product separation and purification cost is high, and the catalyst is difficult to recover. Commonly used solid acid catalysts mainly include molecular sieves, acidic resins, transition metal oxides, phosphates, heteropolyacids, and the like. Although the supported catalyst improves the yield of the furfural to a certain extent compared with homogeneous acid, the catalyst cost is lowThe stability of the body is poor.
The Core-shell type catalyst is a heterogeneous catalyst with great application potential, and is often applied to hydrogenation reaction and catalytic reaction requiring multiple active sites due to the advantages of large specific surface area, regular shape, controllable material size, stable performance, easy recovery and reutilization of products and the like. In the acid catalysis reaction for preparing furfural by catalyzing corncobs, it is unknown how to design the components and the structure of a Core-shell type catalyst so that the catalyst is more favorable for catalyzing the corncobs to synthesize furfural. Therefore, research and development of a novel Core-shell type catalyst, and further improvement of efficiency and yield of the catalyst for catalyzing corncobs to generate furfural become a problem to be solved urgently.
Disclosure of Invention
The invention provides a Core-shell structure M for solving the technical problems of low catalytic efficiency and low furfural yield of the existing Core-shell type catalyst for catalyzing corncobs to generate furfural x O y @mSiO 2 -SO 3 An H-type catalyst, a preparation method thereof and a method for preparing furfural by catalyzing corncobs.
The invention relates to a core-shell structure M x O y @mSiO 2 -SO 3 The H-type catalyst core is spherical metal oxide M x O y The shell is sulfonated mesoporous SiO 2 。
Further defined, the metal oxide is WO 3 、Fe 3 O 4 、Al 2 O 3 Or NiO.
Further defined, the spherical metal oxide M x O y The particle diameter of the shell is 80 nm-150 nm, and the thickness of the shell layer is 10 nm-50 nm.
The invention relates to a core-shell structure M x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst comprises the following steps:
step 1: stirring and mixing CTAB and water at room temperature for 5-30min, dropwise adding an ammonia water solution to adjust the pH value to 9-11, continuously stirring for 5-30min, adding a metal salt, firstly performing ultrasonic treatment for 5-30min, then stirring for 3-6h, then naturally aging for 5-10h, centrifuging deionized water, drying to obtain a metal hydroxide, and roasting the metal hydroxide to obtain a metal oxide;
step 2: mixing metal oxide, CTAB and ethanol solution, performing ultrasonic treatment for 30-60min, adding ammonia water solution to adjust pH to 9-11, adding silicon source, stirring for reaction for 7-9h, and centrifuging to obtain M x O y @SiO 2 Drying overnight and then calcining to obtain M x O y @mSiO 2 ；
And step 3: will M x O y @mSiO 2 Sequentially purifying in deionized water and an organic solvent, adding 3-mercaptopropyltrimethoxysilane (MPTMS) at room temperature while stirring, stirring for 20-28h, performing reflux reaction for 2-5h, cooling, performing suction filtration, and adding dichloromethane for natural air drying;
and 4, step 4: adding methanol into the product obtained in the step (3), performing ultrasonic treatment for 20-60min, adding hydrogen peroxide solution, adding ethanol, centrifuging for 0.1-1h, drying, adding dilute sulfuric acid solution, acidifying for 4-8h, centrifuging, washing and drying to obtain the core-shell structure M x O y @mSiO 2 -SO 3 A catalyst of the H type.
Further defined, the metal salt in step 1 is WCl 6 、FeCl 3 ·6H 2 O、AlCl 3 Or NiCl 2 To (3) is provided.
Further defined, CTAB and H in step 1 2 The mass ratio of O is 1 (30-60), and the molar ratio of CTAB to the metal salt is 1 (1-3).
Further limiting, the roasting process in the step 1 is as follows: heating to 400-600 deg.C at a rate of 1-3 deg.C/min, and maintaining for 2-5h.
Further defined, in step 2, the molar ratio of CTAB to the metal oxide is 1 (0.5-3), and the ratio of the mass of the metal oxide to the volume of the ethanol solution is 1g: (200-300) mL, H in ethanol solution 2 O and C 2 H 5 The volume ratio of OH is 1 (3-5).
Further limiting, in the step 2, the silicon source is one of tetraethyl orthosilicate (TEOS), water glass and silica sol, and the mass ratio of the silicon source to the metal oxide is 1 (1-3).
Further limiting, the roasting process in the step 2 is as follows: heating to 400-600 deg.C at a rate of 1-3 deg.C/min, and maintaining for 2-5h.
Further limiting, the purification process in step 3 is: will M x O y @mSiO 2 Is dispersed in H 2 And in O, refluxing for 2-5h at 80-100 ℃, continuously stirring at the stirring speed of 200-300rpm in the cooling process, performing suction filtration, adding toluene, and performing azeotropic distillation for 2-5h.
Further defined, in step 3, M x O y @mSiO 2 And the mass ratio of MPTMS is 1: (2-6), mass of MPTMS and CH 2 Cl 2 Is 1g: (2-10) mL.
Further limiting, the volume ratio of the methanol in the step 4 to the dichloromethane in the step 3 is 1 (1-2), and H 2 O 2 The volume ratio of the diluted sulfuric acid to the methanol is 1 (3-6), the concentration of the diluted sulfuric acid is 0.05-0.20mol/L, and the volume ratio of the methanol to the diluted sulfuric acid is 1: (2-5).
The invention relates to a core-shell structure M x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
replacing air in the stainless steel high-pressure reaction kettle with nitrogen for several times, and adding M x O y @mSiO 2 -SO 3 H, reacting with the corncob hydrolysate at 140-220 ℃ for 2-5H to obtain furfural.
To be further limited, M x O y @mSiO 2 -SO 3 H accounts for 5-10% of the mass of the corncobs.
Compared with the prior art, the invention has the advantages that:
the invention takes metal oxide as an L acid active site and SiO as 2 -SO on mesoporous shell 3 H is an acid site B, and active sites of the diacid are effectively combined through a core-shell structure, so that the synergistic effect is maximized, the efficiency and the yield of catalyzing the corncobs to produce furfural are remarkably improved, and the method has the following specific advantages:
1) M prepared by the invention x O y @mSiO 2 -SO 3 H-type catalyst with spherical metal oxide as core and sulfonated mesoporous SiO as shell 2 Compared with the prior art, the peach pit-pulp nano structure has hexadecyl trimethyl bromideThe shape of the metal oxide is adjusted by adding ammonium (CTAB), and the spherical metal oxide M is prepared by adjusting the concentration of the metal oxide x O y The purpose of (1).
2) The invention takes metal oxide as L acid active site, the-SO on the shell surface 3 H is used as an active site of the B acid, the B acid and the L acid have a spatial structure through a core-shell structure, the active site of the L acid is surrounded by the B acid at an interface, the active sites of the two acids are effectively combined, not only can cascade catalysis be realized, but also the synergistic effect can be maximized, xylose molecules obtained by hydrolyzing corncobs can be isomerized into xylulose by the L acid after contacting with kernels, and the xylose molecules are isomerized into xylulose by the L acid due to SiO 2 Due to the existence of the mesoporous pore canal, the generated xylulose molecules can be treated by B acid-SO in the pore canal of the shell layer 3 The furfural is generated by removing trimolecular water from H, which is beneficial to the reaction and greatly improves the reaction activity.
3) The invention relates to mesoporous SiO with grafted 3-mercaptopropyl trimethoxy silane (MPTMS) configuration 2 The shell is made of sulfhydryl peroxide as a sulfonic acid group, so that the amount of active sites of the B acid is increased, and the reaction activity is further improved.
4) After the catalytic reaction is finished, the catalyst and the product can be separated simply and efficiently by utilizing a centrifugal mode, the catalyst phase does not need post-treatment and can be directly reused, the catalytic performance is not obviously reduced after the catalyst phase is reused for 10 times, and the recycling effect is good.
Drawings
FIG. 1 shows the preparation of core-shell structure M of the present invention x O y @mSiO 2 -SO 3 A synthetic mechanism diagram of H;
FIG. 2 shows WO obtained in step 1 of example 1 3 A TEM image of (D);
FIG. 3 shows WO obtained in step 1 of example 1 3 The particle size distribution map of (a);
FIG. 4 shows WO obtained in step 2 of example 1 3 @mSiO 2 A TEM image of (B);
FIG. 5 shows the core-shell structure WO obtained in example 1 3 @mSiO 2 -SO 3 TEM images of H-type catalysts;
FIG. 6 is a liquid chromatogram of the reaction solution obtained in application example 1;
FIG. 7 shows the production of furfural by application example 1 1 H NMR；
FIG. 8 shows the production of furfural by application example 1 13 C NMR。
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The experimental procedures used in the following examples are conventional unless otherwise specified. The materials, reagents, methods and apparatus used, unless otherwise specified, are conventional and commercially available to those skilled in the art.
Example 1: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst comprises the following steps:
step 1:
s1, stirring and mixing 2.43g CTAB (6.67 mmol) and 100.00mL of water at room temperature for 30min, dropwise adding 4.00mL of ammonia water solution to adjust the pH to 10, continuing stirring for 5min, and adding 4.64g WCl 6 (11.70 mmol), firstly carrying out ultrasonic treatment for 10min, and then stirring for 4h to obtain WCl 6 A solution;
s2, mixing WCl 6 Naturally aging the solution at room temperature for 7h, centrifuging with deionized water, and drying at 80 deg.C for 12h to obtain metal hydroxide W (OH) 6 ；
S3, adding metal hydroxide W (OH) 6 Roasting, wherein the roasting process comprises the following steps: heating to 500 deg.C at a rate of 1 deg.C/min, and maintaining for 3 hr to obtain metal oxide WO 3 (ii) a Metal oxide WO 3 Shown in FIG. 2, a metal oxide WO 3 The particle size distribution of (A) is shown in FIG. 3, and from FIGS. 2 to 3, it can be seen that the metal oxide WO is shown 3 The particle size distribution of (A) is normal distribution, and the particle size range is mainly between 13nm and 48 nm.
Step 2:
1.40g of WO 3 (6.04mmol)、2.24g CTAB (6.15 mmol) and 350.00mL of ethanol solution (70.00 mL of H 2 O+280.00mL CH 3 CH 2 OH), performing ultrasonic treatment for 60min, then adding 5.00mL of ammonia water solution to adjust the pH value to 10, then adding 0.94g of TEOS, stirring to react for 8h, and centrifuging to obtain WO 3 @SiO 2 And after drying overnight, roasting, wherein the roasting process is as follows: heating to 500 ℃ at the speed of 1 ℃/min, and keeping the temperature for 3 hours to obtain WO 3 @mSiO 2 ；WO 3 @mSiO 2 The TEM image of (A) is shown in FIG. 4, and WO can be seen from FIG. 4 3 @mSiO 2 The surface is successfully grafted with a silicon dioxide shell, and the particle size is increased to more than 100 nm.
And step 3:
s1, adding WO 3 @mSiO 2 Purifying in deionized water and an organic solvent in sequence, wherein the specific process comprises the following steps: 1.53g of WO 3 @mSiO 2 Dispersed in 191.00mL of H 2 Refluxing O at 100 ℃ for 3h, continuously stirring at the stirring speed of 250rpm in the cooling process, performing suction filtration, adding 115.00mL of toluene, and performing azeotropic distillation for 3h;
s2, adding 6.31g of MPTMS while stirring at room temperature, stirring for 24h, performing reflux reaction for 3h, cooling, performing suction filtration, placing in a watch glass, and adding 30.00mL of CH 2 Cl 2 Naturally drying;
and 4, step 4: adding 20.00mL of methanol into the product obtained in the step 3, performing ultrasonic treatment for 30min, then adding 4.40mL of hydrogen peroxide solution with the mass concentration of 35.00%, adding ethanol, centrifuging for 0.5h, drying, adding 50.00mL of dilute sulfuric acid solution with the concentration of 0.10mol/L, acidifying for 5h, centrifuging, washing and drying to obtain the core-shell structure WO 3 @mSiO 2 -SO 3 A catalyst of the H type.
Example 1 core-Shell Structure WO 3 @mSiO 2 -SO 3 The TEM image of H is shown in FIG. 5, and it can be seen from FIG. 5 that WO is applied after introduction of a sulfonic acid group 3 @mSiO 2 -SO 3 The particle size of H is about 100nm, the particle size is not obviously changed, and the silica shell is clearly visible.
Example 2: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst comprises the following steps:
step 1:
s1, stirring and mixing 2.43g CTAB (6.67 mmol) and 100.00mL of water at room temperature for 30min, dropwise adding 4.00mL of ammonia water solution to adjust the pH to 10, continuing stirring for 5min, and adding 4.64g WCl 6 (11.70 mmol), firstly carrying out ultrasonic treatment for 10min, and then stirring for 4h to obtain WCl 6 A solution;
s2, mixing WCl 6 Naturally aging the solution at room temperature for 7h, centrifuging with deionized water, and drying at 80 deg.C for 12h to obtain metal hydroxide W (OH) 6 ；
S3, mixing the metal hydroxide W (OH) 6 Roasting, wherein the roasting process comprises the following steps: heating to 500 deg.C at a rate of 1 deg.C/min, and maintaining for 3 hr to obtain metal oxide WO 3 ；
And 2, step:
1.40g of WO 3 (6.04 mmol), 2.24g CTAB (6.15 mmol) and 350.00mL of ethanol solution (70.00 mL of H) 2 O+280.00mLCH 3 CH 2 OH), performing ultrasonic treatment for 60min, then adding 5.00mL of ammonia water solution to adjust the pH value to 10, then adding 0.94g of TEOS, stirring to react for 8h, and centrifuging to obtain WO 3 @SiO 2 And after drying overnight, roasting, wherein the roasting process is as follows: heating to 500 deg.C at a rate of 1 deg.C/min, and maintaining for 3 hr to obtain WO 3 @mSiO 2 ；
And step 3:
s1, adding WO 3 @mSiO 2 Purifying in deionized water and an organic solvent in sequence, wherein the specific process comprises the following steps: 1.53g of WO 3 @mSiO 2 Dispersed in 191.00mL of H 2 In O, refluxing for 3h at 100 ℃, continuously stirring in the cooling process at the stirring speed of 250rpm, filtering, adding 115.00mL of methylbenzene, and performing azeotropic distillation for 3h;
s2, adding 4.38g of MPTMS while stirring at room temperature, stirring for 24h, performing reflux reaction for 3h, cooling, performing suction filtration, placing in a watch glass, and adding 12.00mL of CH 2 Cl 2 Naturally drying;
and 4, step 4: adding 20.00mL of methanol into the product obtained in the step 3, performing ultrasonic treatment for 30min, then adding 3.40mL of hydrogen peroxide solution with the mass concentration of 35.00%, adding ethanol, centrifuging for 0.15h, drying, and adding 37.00mL of 0.10mol/L dilute solutionAcidifying with sulfuric acid solution for 5h, centrifuging, washing and drying to obtain core-shell structure WO 3 @mSiO 2 -SO 3 A catalyst of the H type.
Example 3: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst comprises the following steps:
step 1:
s1, stirring and mixing 2.43g CTAB (6.67 mmol) and 100.00mL of water at room temperature for 30min, dropwise adding 4.00mL of ammonia water solution to adjust the pH to 10, continuing to stir for 5min, adding 3.16g of FeCl 3 ·6H 2 O (14.61 mmol), firstly carrying out ultrasonic treatment for 10min, and then stirring for 4h to obtain FeCl 3 A solution;
s2, feCl 3 Naturally aging the solution at room temperature for 7h, centrifuging with deionized water, and drying at 80 deg.C for 12h to obtain metal hydroxide Fe (OH) 3 ；
S3, mixing metal hydroxide Fe (OH) 3 Roasting, wherein the roasting process comprises the following steps: heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 3h to obtain metal oxide Fe 3 O 4 ；
Step 2:
1.39g of Fe 3 O 4 (6.00 mmol), 2.24g CTAB (6.15 mmol) and 350.00mL of ethanol solution (70.00 mL of H) 2 O+280.00mL CH 3 CH 2 OH), performing ultrasonic treatment for 60min, then adding 5.00mL of ammonia water solution to adjust the pH value to 10, then adding 0.94g of TEOS, stirring to react for 8h, and centrifuging to obtain Fe 3 O 4 @SiO 2 And after drying overnight, roasting, wherein the roasting process is as follows: heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 3h to obtain Fe 3 O 4 @mSiO 2 ；
And 3, step 3:
s1, mixing Fe 3 O 4 @mSiO 2 Purifying in deionized water and an organic solvent in sequence, wherein the specific process comprises the following steps: 1.53g of Fe 3 O 4 @mSiO 2 Dispersed in 191.00mL of H 2 In O, refluxing for 3h at 100 ℃, continuously stirring in the cooling process at the stirring speed of 250rpm, filtering, adding 115.00mL of methylbenzene, and performing azeotropic distillation for 3h;
S2adding 6.31g of MPTMS at room temperature while stirring, stirring for 24h, carrying out reflux reaction for 3h, cooling, carrying out suction filtration, placing in a watch glass, and adding 30.00mL of CH 2 Cl 2 Naturally drying;
and 4, step 4: adding 20.00mL of methanol into the product obtained in the step 3, performing ultrasonic treatment for 30min, then adding 4.40mL of hydrogen peroxide solution with the mass concentration of 35.00%, adding ethanol, centrifuging for 1h, drying, adding 50.00mL of dilute sulfuric acid solution with the concentration of 0.10mol/L, acidifying for 5h, centrifuging, washing and drying to obtain the core-shell structure Fe 3 O 4 @mSiO 2 -SO 3 A catalyst of the H type.
Example 4: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst comprises the following steps:
step 1:
s1, stirring and mixing 2.43g CTAB (6.67 mmol) and 100.00mL of water at room temperature for 30min, dropwise adding 4.00mL of ammonia water solution to adjust the pH to 10, continuing stirring for 5min, adding 1.56g of AlCl 3 (11.70 mmol), firstly carrying out ultrasonic treatment for 10min, and then stirring for 4h to obtain AlCl 3 A solution;
s2, mixing AlCl 3 Naturally aging the solution at room temperature for 7h, centrifuging with deionized water, and drying at 80 deg.C for 12h to obtain metal hydroxide Al (OH) 3 ；
S3, mixing metal hydroxide Al (OH) 3 Roasting, wherein the roasting process comprises the following steps: heating to 500 deg.C at a rate of 1 deg.C/min, and maintaining for 3 hr to obtain metal oxide Al 2 O 3 ；
Step 2:
0.61g of Al 2 O 3 (5.98 mmol), 2.24g CTAB (6.15 mmol) and 350.00mL of ethanol solution (70.00 mL of H) 2 O+280.00mL CH 3 CH 2 OH), performing ultrasonic treatment for 60min, then adding 5.00mL of ammonia water solution to adjust the pH value to 10, then adding 0.94g of TEOS, stirring to react for 8h, and centrifuging to obtain Al 2 O 3 @SiO 2 And after drying overnight, roasting, wherein the roasting process is as follows: heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 3h to obtain Al 2 O 3 @mSiO 2 ；
And step 3:
s1, mixing Al 2 O 3 @mSiO 2 Purifying in deionized water and an organic solvent in sequence, wherein the specific process comprises the following steps: 1.53g of Al 2 O 3 @mSiO 2 Dispersed in 191.00mL of H 2 Refluxing O at 100 ℃ for 3h, continuously stirring at the stirring speed of 250rpm in the cooling process, performing suction filtration, adding 115.00mL of toluene, and performing azeotropic distillation for 3h;
s2, adding 6.31g of MPTMS while stirring at room temperature, stirring for 24h, performing reflux reaction for 3h, cooling, performing suction filtration, placing in a watch glass, and adding 30.00mL of CH 2 Cl 2 Naturally drying;
and 4, step 4: adding 20.00mL of methanol into the product obtained in the step 3, performing ultrasonic treatment for 30min, then adding 4.40mL of hydrogen peroxide solution with the mass concentration of 35.00%, adding ethanol, centrifuging for 1h, drying, adding 50.00mL of dilute sulfuric acid solution with the concentration of 0.10mol/L, acidifying for 5h, centrifuging, washing and drying to obtain the Al with the core-shell structure 2 O 3 @mSiO 2 -SO 3 A catalyst of the H type.
Application example 1: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing corn cob hydrolysate:
taking 1g of corncob crushed to 100 meshes, drying at 80 ℃, then placing the corncob into a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL of oxalic acid solution (0.5 wt%), reacting at 140 ℃ for 40min, after the reaction, carrying out solid-liquid separation by centrifugal filtration, and concentrating the liquid phase by a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen gas 5 times, 0.05g of WO prepared in example 1 was added 3 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, adding 10.00mL of toluene, reacting at 180 ℃ for 4H, standing and cooling to room temperature to obtain a reaction solution, extracting and layering by using a water phase and an organic phase reaction solution, separating a product in an organic phase and a catalyst in a water phase, and separatingThe post catalyst can be directly recycled without post treatment.
The liquid chromatogram of the obtained reaction solution is shown in fig. 6, and it can be seen from fig. 6 that furfural was successfully synthesized.
Application example 2: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing corn cob hydrolysate:
taking 1g of corncob crushed to 100 meshes, drying at 80 ℃, then placing the corncob into a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL of oxalic acid solution (0.5 wt%), reacting at 140 ℃ for 40min, after the reaction, carrying out solid-liquid separation by centrifugal filtration, and concentrating the liquid phase by a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen gas 5 times, 0.05g of WO prepared in example 2 was added 3 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, 10.00mL of toluene is added, the reaction is carried out for 5H at 150 ℃, the mixture is kept stand and cooled to room temperature to obtain reaction liquid, the water phase and the organic phase are used for carrying out extraction and layering, the product is in the organic phase, the catalyst is in the water phase, and the separated catalyst can be directly recycled without post-treatment.
Application example 3: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing a corn cob hydrolysate:
taking 1g of corncobs crushed to 100 meshes, drying the corncobs at 80 ℃, then placing the corncobs in a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL oxalic acid solution (0.5 wt%), reacting for 40min at 140 ℃, separating solid from liquid through centrifugal filtration after reaction, and concentrating the liquid phase through a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen 5 times, 0.08g of Fe prepared in example 3 was added 3 O 4 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, 10.00mL of toluene is added, the reaction is carried out for 5H at 150 ℃, the mixture is kept stand and cooled to room temperature to obtain reaction liquid, the water phase and the organic phase are used for carrying out extraction and layering, the product is in the organic phase, the catalyst is in the water phase, and the separated catalyst can be directly recycled without post-treatment.
Application example 4: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing corn cob hydrolysate:
taking 1g of corncob crushed to 100 meshes, drying at 80 ℃, then placing the corncob into a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL of oxalic acid solution (0.5 wt%), reacting at 140 ℃ for 40min, after the reaction, carrying out solid-liquid separation by centrifugal filtration, and concentrating the liquid phase by a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen 5 times, 0.07g of Al prepared in example 4 was added 2 O 3 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, adding 10.00mL of toluene, reacting for 3H at 160 ℃, standing and cooling to room temperature to obtain a reaction solution, extracting and layering by utilizing a water phase and an organic phase reaction solution, wherein a product is in the organic phase, a catalyst is in the water phase, and the separated catalyst can be directly recycled without aftertreatment.
Application example 5: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing corn cob hydrolysate:
taking 1g of corncob crushed to 100 meshes, drying at 80 ℃, then placing the corncob into a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL of oxalic acid solution (0.5 wt%), reacting at 140 ℃ for 40min, after the reaction, carrying out solid-liquid separation by centrifugal filtration, and concentrating the liquid phase by a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen 5 times, 0.05g of WO prepared in example 1 was added 3 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, 10.00mL of toluene is added, the reaction is carried out for 2H at 220 ℃, the mixture is kept stand and cooled to room temperature to obtain reaction liquid, the water phase and the organic phase are used for carrying out extraction and layering, the product is in the organic phase, the catalyst is in the water phase, and the separated catalyst can be directly recycled without post-treatment.
Application example 6: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst comprises the following steps:
s1, preparing a corn cob hydrolysate:
taking 1g of corncob crushed to 100 meshes, drying at 80 ℃, then placing the corncob into a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL of oxalic acid solution (0.5 wt%), reacting at 140 ℃ for 40min, after the reaction, carrying out solid-liquid separation by centrifugal filtration, and concentrating the liquid phase by a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen gas 5 times, 0.07g of WO prepared in example 1 was added 3 @mSiO 2 -SO 3 H and 5.00mL of corncob hydrolysate, 10.00mL of toluene is added, the reaction is carried out for 4H at 180 ℃, the mixture is kept stand and cooled to room temperature to obtain reaction liquid, the water phase and the organic phase are used for carrying out extraction and layering, the product is in the organic phase, the catalyst is in the water phase, and the separated catalyst can be directly recycled without post-treatment.
Application example 7: core-shell structure M of the embodiment x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with H-type catalyst comprises the following stepsCarrying out the following steps:
s1, preparing corn cob hydrolysate:
taking 1g of corncobs crushed to 100 meshes, drying the corncobs at 80 ℃, then placing the corncobs in a 100mL high-temperature high-pressure stainless steel reactor, adding 80mL oxalic acid solution (0.5 wt%), reacting for 40min at 140 ℃, separating solid from liquid through centrifugal filtration after reaction, and concentrating the liquid phase through a rotary evaporator until the xylose concentration is 5wt%, namely the corncob hydrolysate.
S2, preparing furfural:
after replacing the air in the stainless steel autoclave with nitrogen 5 times, 0.05g of WO prepared in example 1 was added 3 @mSiO 2 -SO 3 And H, recycling the recovered catalyst and 5.00mL of corncob hydrolysate after 10 times, adding 10.00mL of toluene, reacting for 4H at 180 ℃, standing and cooling to room temperature to obtain a reaction solution, performing extraction and layering by using a water phase and an organic phase reaction solution, wherein the product is in an organic phase, the catalyst is in a water phase, and the separated catalyst can be directly recycled without aftertreatment.
The furfural yield is calculated by the following formula:
m 1 ＝m f +M f
m f ＝C f ×V f
wherein Y is the yield of furfural; m is 1 Actual mass of furfural produced for the reaction; m is a unit of 2 Theoretical mass of furfural that can be made from corncobs; m is a unit of f Is the mass of furfural in the organic phase; w is a f Is the substance of furfural in water phaseAn amount; c f The mass concentration of furfural in the organic phase is g/mL; v f The volume of the organic phase; the distribution ratio of the furfural in the organic phase and the water phase is 10.6:1; m is a unit of Corn cob The mass of the corncobs added into the reaction kettle; m Furfural Represents the molar mass of furfural, 96.09g/mol; m Xylose (XO) Represents the molar mass of xylose, 150.03g/mol;0.27 is that the corncob contains 27.00 percent of xylose.
The furfural yields obtained in application examples 1-10 are shown in Table 1.
TABLE 1 Furfural yield
Claims (10)
1. Core-shell structure M x O y @mSiO 2 -SO 3 H-type catalyst, characterized in that the catalyst core is a spherical metal oxide M x O y The shell is sulfonated mesoporous SiO 2 。
2. Core-shell structure M according to claim 1 x O y @mSiO 2 -SO 3 H-type catalyst, characterized in that the metal oxide is WO 3 、Fe 3 O 4 、Al 2 O 3 Or NiO.
3. Core-shell structure M according to claim 1 x O y @mSiO 2 -SO 3 H-type catalyst, characterized in that the spherical metal oxide M x O y The grain diameter of the shell is 80 nm-150 nm, and the thickness of the shell is 10 nm-50 nm.
4. A core-shell structure M as claimed in any of claims 1 to 3 x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst is characterized by comprising the following steps:
step 1: stirring and mixing CTAB and water at room temperature for 5-30min, dropwise adding an ammonia water solution to adjust the pH value to 9-11, continuously stirring for 5-30min, adding a metal salt, firstly performing ultrasonic treatment for 5-30min, then stirring for 3-6h, then performing natural aging for 5-10h, centrifuging deionized water, drying to obtain a metal hydroxide, and roasting the metal hydroxide to obtain a metal oxide;
and 2, step: mixing metal oxide, CTAB and ethanol solution, performing ultrasonic treatment for 30-60min, adding ammonia water solution to adjust pH to 9-11, adding silicon source, stirring for reaction for 7-9h, and centrifuging to obtain M x O y @SiO 2 Drying overnight and then calcining to obtain M x O y @mSiO 2 ；
And step 3: will M x O y @mSiO 2 Sequentially purifying in deionized water and an organic solvent, then adding MPTMS under stirring at room temperature, stirring for 20-28h, performing reflux reaction for 2-5h, cooling, performing suction filtration, adding dichloromethane, and naturally drying;
and 4, step 4: adding methanol into the product obtained in the step (3), performing ultrasonic treatment for 20-60min, adding hydrogen peroxide solution, adding ethanol, centrifuging for 0.1-1h, drying, adding dilute sulfuric acid solution, acidifying for 4-8h, centrifuging, washing and drying to obtain the core-shell structure M x O y @mSiO 2 -SO 3 A catalyst of the H type.
5. Core-shell structure M according to claim 4 x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst is characterized in that the metal salt in the step 1 is WCl 6 、FeCl 3 ·6H 2 O、AlCl 3 Or NiCl 2 One of them, CTAB and H 2 The mass ratio of O is 1 (30-60), the molar ratio of CTAB to metal salt is 1 (1-3), and the roasting process is as follows: heating to 400-600 deg.C at a rate of 1-3 deg.C/min, and maintaining for 2-5h.
6. Core-shell structure M according to claim 4 x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst is characterized in that the molar ratio of CTAB to the metal oxide in the step 2 is 1 (0.5-3), and the mass of the metal oxide and the volume of the ethanol solutionThe ratio of (1 g): (200-300) mL, H in ethanol solution 2 O and C 2 H 5 The volume ratio of OH is 1 (3-5), the silicon source is one of TEOS, water glass and silica sol, the mass ratio of the silicon source to the metal oxide is 1 (1-3), and the roasting process is as follows: heating to 400-600 deg.C at a rate of 1-3 deg.C/min, and maintaining for 2-5h.
7. Core-shell structure M according to claim 4 x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst is characterized in that the purification process in the step 3 is as follows: will M x O y @mSiO 2 Is dispersed in H 2 Refluxing O at 80-100 deg.C for 2-5 hr, stirring at 200-300rpm during cooling, vacuum filtering, adding toluene, azeotropic distilling for 2-5 hr, and distilling at M x O y @mSiO 2 And the mass ratio of MPTMS is 1: (2-6), quality of MPTMS and CH 2 Cl 2 Is 1g: (2-10) mL.
8. Core-shell structure M according to claim 4 x O y @mSiO 2 -SO 3 The preparation method of the H-type catalyst is characterized in that the volume ratio of the methanol in the step 4 to the dichloromethane in the step 3 is 1 (1-2), and H is 2 O 2 The volume ratio of the diluted sulfuric acid to the methanol is 1 (3-6), the concentration of the diluted sulfuric acid is 0.05-0.20mol/L, and the volume ratio of the methanol to the diluted sulfuric acid is 1: (2-5).
9. A core-shell structure M as claimed in any of claims 1 to 3 x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with the H-type catalyst is characterized by comprising the following steps:
replacing the air in the stainless steel high-pressure reaction kettle with nitrogen for a plurality of times, and adding M x O y @mSiO 2 -SO 3 H, reacting with the corncob hydrolysate at 140-220 ℃ for 2-5H to obtain the furfural.
10. Core-shell structure M according to claim 9 x O y @mSiO 2 -SO 3 The method for preparing furfural by catalyzing corncobs with H-type catalyst is characterized in that M x O y @mSiO 2 -SO 3 H accounts for 5-10% of the mass of the corncobs.
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| US20190009255A1 (en) * | 2017-07-05 | 2019-01-10 | Hangzhou Normal University | Core-shell structure supported tungsten composite catalyst and preparation method and use thereof |
| CN109776460A (en) * | 2019-03-27 | 2019-05-21 | 北京林业大学 | A method of Furfural Production from Xylose is catalyzed using solid acid catalyst |
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| CN103433032A (en) * | 2013-09-18 | 2013-12-11 | 安徽工业大学 | WO3@mSiO2 microballoon sphere with nuclear shell hollow structure as well as preparation method and application thereof |
| CN104230860A (en) * | 2014-09-28 | 2014-12-24 | 华南理工大学 | Method for preparing furfural by catalyzing corncobs by two-section process |
| US20190009255A1 (en) * | 2017-07-05 | 2019-01-10 | Hangzhou Normal University | Core-shell structure supported tungsten composite catalyst and preparation method and use thereof |
| CN109126841A (en) * | 2018-08-10 | 2019-01-04 | 太原理工大学 | It is a kind of to prepare hud typed VPO@SiO2The method of catalyst |
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| ISLAM ELSAYED ET AL.: "Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst", FUEL, vol. 221, pages 2 * |
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